Journal of the Korean Chemical Society (대한화학회지)

Korean Chemical Society (대한화학회)
권호 표지

The Reactivity and Regiochemical Effect of Nitrosonium Species in the Nitrosation of N-Methyl-N'-Substituted Phenylureas

N-메틸-N'-치환페닐우레아화합물들의 니트로소화 반응에 있어서 니트로소화 화학종의 반응성 및 위치화학적 영향

  • Jack C. Kim (Department of Chemistry, Pusan National University) ;
  • In-Seop Cho (Department of Chemistry, Pusan National University) ;
  • Soon-Kyu Choi (Department of Chemistry, Dong-A University)
  • 김정균 (부산대학교 자연과학대학 화학과) ;
  • 조인섭 (부산대학교 자연과학대학 화학과) ;
  • 최순규 (동아대학교 자연과학대학 화학과)
  • Published : 1991.06.20
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Abstract

The regioselectivity in the nitrosation of seven N-methyl-N'-substituted phenylureas ($CH_3NHCONHC_6H_4-G$; G = H, p-CH$_3$, m-CH$_3$, m-CH$_3$O, p-F, m-F, m-Br) was examined using NaNO$_2$ and 4 different acids (diluted HCl, HCOOH, CH$_3$COOH, CF$_3$COOH). In all cases, the two regioisomeric products, N-nitroso-N-methyl-N'-substituted phenylureas (A) and N'-nitroso-N-methyl-N'-substituted phenylureas (B) were observed to be formed as major products and product ratios were determined by the integration of their methyl peaks in $^1$H-NMR. Electron donating substitutent(G) on phenyl of the ureas generally led to increase the ratio of B to A. The data have revealed that the relative sensitivity of the nitrosonium species (HONO, HCOONO, CH$_3$COONO, CF$_3$COONO) toward the change of electron density on nitrogen with phenyl substitutents are 1.00 : 0.93 : 0.78 : > ∼ 0.7.

비대칭우레아화합물, N-메틸-N'-치환페닐우레아화합물들 ($CH_3NHCONHC_6H_4-G$; G = H, p-$CH_3,\;m-CH_3,\;m-CH_3O$, p-F, m-F, m-Br) 7종 합성하고 이들을 NaN$O_2$와 4종류의 산(d-HCl, HCOOH, C$H_3$COOH, CF$_3$COOH)을 사용하여 니트로소화시킬 때 이 니트로소화 반응의 위치선택성을 조사하였다. 이들 반응 모든 경우에서 두 가지 위치이성질체생성물, N-니트로소-N-메틸-N'-치환페닐우레아생성물(A)들과 N'-니트로소-N-메틸-N'-치환페닐우레아생성물(B)들이 주생성물로 생성되었으며, 이들 생성몰비 B/A를 이들 반응혼합물의 $^1$H-NMR에서의 메틸피이크의 면적을 측정하여 이를 결정하였다. 전자공급체치환기(ㅎ)가 우레아화합물의 페닐기에 치환된 경우 일반적으로 B/A의 비가 증가되었다. 이들 위치이성체 생성물비 B/A로부터 니트로소화 화학종(HONO, HCOONO, CH$_3$ COONO, CF$_3$ COONO)의 페닐치환기에 의한 질소원자 위의 전자밀도변화에 대한 반응민감도를 얻었으며 반응민감도의 상대적 크기는 1.00 : 0.93 : 0.78 : > ∼ 0.7(HONO : HCOONO : CH$_3$ COONO : CF$_3$ COONO)로 나타났다.

Keywords

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